3-(3-chloro-2 -propenyl)-1,3,5,7-tetraazabicyclo(3.3.1) nonane-3-methanol and its preparation

ABSTRACT

7-Cis- or 7-cis-trans-(3-Chloro-2-propenyl)-1,3,5,7tetraazabicyclo(3.3.1)nonane-3 -methanol is prepared by reacting cis-, or cis-trans- 7-(3-chloro-2-propenyl)-3,5,7-triaza-1azoniatricyclo(3.3.1.13,7)decane chloride with excess aqueous strong base at room temperature to give the corresponding carbinolamine, 7-(3-chloro-2-propenyl)-1,3,5,7tetraazabicyclo(3.3.1)nonane-3-methanol.

United States Patent 1 Jan. 28, 1975 TETRAAZABICYCLO(3.3.] NONANE-3-METHANOL AND ITS PREPARATION [75] Inventor: Thomas P. Brady, Nutick, Mass.

[73] Assignee: The Dow Chemical Company,

Midland, Mich.

[221 Filed: Oct. 23, 1973 [21] Appl. No.: 408,889

[52] US. Cl. 260/248 NS, 424/249 [51] Int. Cl C07d 55/14 [58] Field of Search 260/248 NS [56] References Cited UNITED STATES PATENTS 3,228,829 H1966 Wolf et ul. 260/248 X Primary Examiner.|0hn M. Ford Attorney, Agent. or Firm-Theodore Post; C. Kenneth Bjork [57} ABSTRACT 7-Cisor 7-cis-truns-(3-Chluro-2-pmpcnyl I 35.7- tctraazabicyclo( 3.3.1 )nonunc-3-miethannl is prepared by reacting cis-. or cis-trans- 7-(3-chloro-2-propcnyl)- 3,5,7-triazu-l-uzoniatricycl0(3.3.1 .l' )dccanc chloride with excess aqueous strong base at room temperature to give the corresponding carbinolaminc. 7-( 3 chl0r0-2-propenyl l ,3,5 ,7-tetraazabicycl0( 3.3.1 )no nane-3-methanol.

4 Claims, N0 Drawings chloro-2-propenyl)-3,5,7-triaza-lazoniatricy- 3 ,8 62 ,9 3 9 l 2 3-(3-CHLORO-2 NaOl-l (0.4 mole) in 100 ml. of H and the reaction -PROPENYL)-l,3,S,7-TETRAAZABICYCLO(3.3.1) mixture stirred about 15 minutes at room temperature. NONANE-3-METHANQL ITREPARATIO The oily aqueous reaction mixture was extracted twice with 200 ml. portions of Cll Cl and the phases allowed BACKGROUND OF THE INVENTION to separate. The Cl-l Cl phases were drawn off in a The art describes the conversion of Nmethyl hexa separatory funnel and dried w|th molecular sieves. The

methylene tetramine salts to form in low yields the N- methyl hexamethylene tetramine hydroxide; US. Pat. iyiiq q f i P iic No. 1,336,709, Apr. 13, 1920 and Foss et al., J. Chem. 10

$00., 1950, 624. Neither reference shows any utility for EXAMPLE 2 the resulting hydroxide. In the first reference, a solu- 100 Grams (0.4 mole) of cis-l-(3-chloro-2- tion of barium hydroxide is used to react with the N- propenyl)-3,5,7-triaza-l-azoniatric:yclo(3.3.l.l )decmethyl hexamethylenetetramine salt, while in the seC- ane chloride was added slowly to a solution of 80 grams 0n reference, moist ilver oxide i e (2.0 mole) NaOH dissolved in 500 ml. H 0 and the re- SUMMARY OF THE INVENTION action mixture stirred l5 minutes at room temperature. Product crs-Carbrnolamrne was extracted with ben- ThlS invention concerns the novel compounds 7-clszene, dried over M12304 and the benzene evaporated to and give 72 grams (78% yield) at a viscous oil, cistetraazabicyclo(3.3.l )nonane-3-methanol, hereinafter referred to as Carbinolamine" or Carbinolamines. The Carbinolamines are prepared by reacting cis-l-(3- Carbinolamine.

The procedures of Example 1 and 2 when repeated with Dowicil 100 give cis-trans- Carbinolamine product.

l 3.3. c o( 1 l )decane chlondfi commerclany avallable The Carbinolamines of this invention have antimicroas Dowicil 200 or cis-transl 3-chloro- 2-prop yl)-3,5,7 i p w a,1 bial activity. In representativeoperations, both the cis decane hl id commercially available as Dowicil and the cis-trans- Carbinolamines when tested for anti- 100, with excess aq strong b an lk li microbial activity using conventional agar dilution tests metal hydroxide such as sodium hydroxid or t give complete growth inhibition against Staphylococcus sium hydroxide r th r strong wat rl bl ba t aureus and Aerobacter aerogenes at a concentration of substantially room temperature, i.e., at or slightly ppm. and against Pseudomonas aeruginosa at 75 below 25C., according to the following equation p.p.m.

N v /N crr oa C H CH 2 2 /N-CH 2-CH=CHC 1 2 w llin the reaction, up to about 5 moles of base per mole What is claimed is: of starting cisor cis-transcompound (I) are used,and 1. A member of the group consisting of fiiiiiiiliaiiiig 2:21.isass?ziaszzs lsaii binolamine product is extracted from the reaction me- 50 nane'3'methanol and dium with a water-immiscible organic solvent, such as pmpenyl)lr3r5r7'tetraazablcycloi3-3-1)noflanemethylene chloride or benzene, to give in high yield the 3methanol- Carbinolamines as high boiling viscous oils, slightly im- 2 7 c miscible with water but highly soluble in organic soltetraazabicyclo (3 3l l )nonaneamethanoL vents such as aromatic solvents, chlorinated hydrocar- 3 bons, ethers, alcohols and ketones. The structures of the Carbinolamines are confirmed by proton and C a nuclear magnetic resonance spectra, and by mass spec- 4. A method for making a cisor a mixture of cisand trometry. trans-7-( 3-chloro-2-propenyl l ,3 ,5 ,7-tetraazabicyclo- DESCRIPTION OF THE EMBODIMENTS (3.3.1)nonane-3-methanol which comprises reacting at room temperature crsor cis-tr'ansl-(3-chloro-2- The following examples and teachings additionally propenyl)- 7-Cis-trans-(3-chloro-2-propenyl)-l,3,5,7- tetraazabicyclo(3.3.l )nonane-B-rnethanol.

describe specific embodiments and the best mode con- 3,57 triaza 1azoniatricyclfl a.1 chIoride templated by the inventor of carrying out the invention. with excess aqueous Strong base and recovering the EXAMPLE 1 spective product 7-(3-chloro-2-propenyl)-l,3,5,7-

tetraazabicyclo-(3.3.l)nonane-3-methanol from the 50.0 Grams of cis-l-(3-chloro-2-propenyl)-3,5,7- reaction medium triaza-l-azoniatricyclo(3.3. l,l )decane chloride (0.2 mole) was added gradually to a solution of 16.0 grams CH Cl was removed in vacuo, 40l20 mm. mercury, to

@2 3 UNITED STATES PATENT OFFICE CRTIFICATE OF CORRECTION Patent No. 3, 862 939 Dated January 28 1975 lnventofls) Thomas P. Brady It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

The title, first and second occurrence, pages 1 and 2, should read "7- (3-CHLORO-2-PROPENYL) l, 3, 5, 7-TETRAAZA- BICYCLO (3 3 l) NONANE-B-METHANOL AND ITS PREPARATION" instead of "3(3" etc.

Column 1, lines 25 and 27, immediately following the trademark "Dowicil" there should be inserted the omitted trademark symbol Column 1, in the paragraph heading "DESCRIPTION OF THE EMBODIMENTS" the word "PREFERRED" was omitted and the heading should read --DESCRIPTION OF THE PREFERRED EMBODIMENTS-.

Column 2, line 23, immediately following the trademark "Dowicil" there should be inserted the omitted trademark symbol Column 2, line 63, there is omitted a bond between the "l" and "azoniatricylco" and the line slgould read -3,5,7-triaza-l-azoniatricyclo(3.3.1.1 )decane chloride--.

Signed and sealed this 20th day of May 1975.

(SEAL) Attest I c. MARSHALL DANN RUTH C, MASON Commissioner of Patents Arresting Officer and Trademarks 

2. 7-Cis-(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo-(3.3.1)nonane-3 -methanol.
 3. 7-Cis-trans-(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane-3 -methanol.
 4. A method for making a cis- or a mixture of cis- and trans-7-(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo-(3.3.1)nonane-3 -methanol which comprises reacting at room temperature cis- or cis-trans- 1-(3-chloro-2-propenyl)-3,5,7-triaza-1azoniatricyclo(3.3.1.13,7)decane chloride with excess aqueous strong base and recovering the respective product 7-(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo-(3.3.1)nonane-3-methanol from the reaction medium. 